CN102361717A - 纳米结构的钙-银磷酸盐复合粉末、用于获得所述粉末的方法以及其杀菌和杀真菌应用 - Google Patents
纳米结构的钙-银磷酸盐复合粉末、用于获得所述粉末的方法以及其杀菌和杀真菌应用 Download PDFInfo
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Abstract
本发明涉及纳米结构的钙-银磷酸盐复合粉末,所述复合粉末可以用作杀菌剂和/或杀真菌剂,具有与商用产品相似的效能且具有低的毒性。本发明还涉及用于获得所述纳米结构的钙-银磷酸盐复合粉末的方法,所述方法包括通过溶胶-凝胶法制备纳米磷酸钙然后在其表面上沉积银纳米颗粒。所述纳米结构粉末可以用于制造适于用作通用消毒剂的杀菌剂和/或杀真菌剂组合物以用于例如外科植入、公共设施、食品、牙科、油漆、衣服和包装。
Description
技术领域
在外科植入部门(部分,区,sector)、公共设施(卫生间和医院、运输工具等)、空调设备、食品、牙科、油漆、衣服和包装(食品、家用、药物、医疗设备等)中的杀菌和杀真菌应用。
背景技术
低浓度的银对广范围的病原体的杀菌性能以及其对哺乳动物细胞的无毒性是熟知的,所述病原体包括是造成植入相关感染的原因的普通菌株。包含银作为抗菌物质的大部分生物材料由两者均由有机和无机基体负载的元素或阳离子形式的金属组成。在含银的聚合物和生物玻璃的情况下已经对抗菌活性进行了研究,但是在纳米结构的钙-银磷酸盐复合材料的情况下未进行研究。
近年来,已经公布了对使用离子交换方法(溶胶-凝胶或共沉淀)获得具有银的羟基磷灰石(HA)化合物的研究。[Han I-H,Lee I-S,Song J-H,Lee M-H,Park J-C,Lee G-H,Sun X-D,Chung S-M.Characterization of asilver-incorporated calcium phosphate film by RBS and its antimicrobialeffects(含银磷酸钙膜由RBS的表征及其抗菌效果).Biomed.Mater.(生物医学材料)2007;2(3):S91-4;Chen W,Oh S,Ong A P,Oh N,Liu Y,Courtney H S,Appleford M and Ong J L 2007 J. Biomed.Mater.Res.A(生物医学材料研究杂志A)82899;Cheng R J,Hsieh M F,Huang K C,Perng L H,Chou F I and Chin T S 2005 Journal of Solid Science and Technology(固体科学与技术杂志)33229;Rameshbabu N,Sampath Kumar T S,Prabhakar T G,Sastry V S,Murty K V G K and Prasad Rao K 2007 J. Biomed. Mater. Res.A(生物医学材料研究杂志A)80581]。这些途径意指银对钙的取代,从而获得钙缺乏的羟基磷灰石。对这些材料的抗菌反应良好,但是已观察到了两个主要缺点:i)钙缺乏能够对HA纳米颗粒的结构稳定性和HA的骨传导能力具有负面影响,以及ii)根据pH,银可能比所期望的释放更快。这导致对作为杀菌源的银纳米颗粒的兴趣增加,因为它们在水介质中的溶解度低。
银纳米颗粒的杀菌活性(杀生物活性,biocidal activity)受到其尺寸的影响:尺寸越小,抗微生物活性越大,为此,存在纳米颗粒团聚的问题。用于避免这种缺点的方案是使用附着于不同基质表面的纳米颗粒而作用。
发明内容
简要描述
本发明的一个目的由纳米复合或纳米结构粉末组成,所述纳米复合或纳米结构粉末在下文中称作本发明的纳米复合材料,其由磷酸钙和附着于其表面的Ag纳米颗粒形成,所述磷酸钙优选具有小于150nm的粒度,所述银纳米颗粒的尺寸优选小于50nm。
本发明的一个特别目的由纳米复合粉末组成,其中磷酸钙以实例且并不旨在限制本发明范围的方式属于下列组:羟基磷灰石,α-TCP,β-TCP和/或它们的组合,优选羟基磷灰石(HA)。
本发明的另一个目的由用于获得本发明纳米复合粉末的方法组成,所述方法在下文中称作本发明的方法,其包括下列步骤:
a.通过溶胶-凝胶加工途径制备纳米磷酸钙;以及
b.在所述磷酸钙表面上沉积银纳米颗粒。
本发明的另一个目的由本发明的纳米复合粉末在杀菌剂和/或杀真菌剂复合材料的精心制作(加工,制造,elaboration)中的应用组成,所述杀菌剂和/或杀真菌剂复合材料可以被用作用于下述应用的通用消毒剂,所述应用以实例且并不旨在限制本发明范围的方式属于下列组:外科植入、公共设施(卫生间和医院、运输工具等)、食品、牙科、油漆、衣服和包装(食品、药物、医疗设备)。
详细说明
在本发明中,纳米结构粉末经描述由小于140nm尺寸的HA纳米颗粒与附着于表面并均匀分散的金属Ag纳米颗粒形成,所述金属Ag纳米颗粒具有小于50nm的粒度(图1和图2),基于作为基质的磷酸钙与在其表面上的银纳米颗粒,所述纳米结构粉末具有杀菌和杀真菌活性。此外,提出了一种可替换的方法,所述方法简单且廉价,用于获得所述纳米结构复合材料,更具体地说,使用两种不同方法(实施例1)。
由本发明提供的相对于现有技术目前状态的第一优势由因为纳米颗粒附着于基质表面而避免了纳米颗粒团聚的事实组成。第二优势是其与商用产品相似的杀菌和杀真菌效能(实施例2)。第三优势是其毒性低并具有相似的效能,毒性低由下述观察证明:与在Vitelinate(约800-1300ppm)的情况下相比,在HA/Ag(<5ppm)的情况下,该材料浸出少于两个数量级的银,这意指远低于商用产品且极远低于毒性水平(银的用量为按重量计约1%)的毒性(实施例2)。另外,与在其中已经用Ag取代Ca的材料的情况下相比,以更加缓慢且可控的方式释放银,这由浸出的银的定量分析显示。因此,考虑到钙和银在杀菌和杀真菌行为上的协同效应,这种新材料可以用作通用消毒剂。
因此,本发明的一个目的由纳米复合或纳米结构粉末组成,所述纳米复合或纳米结构粉末在下文中称作本发明的纳米复合材料,其由磷酸钙组成,所述磷酸钙优选具有小于150nm的粒度且具有附着于其表面的Ag纳米颗粒,所述银纳米颗粒的尺寸优选小于50nm。
本发明的一个特别目的由纳米复合粉末组成,其中磷酸钙以实例且并不旨在限制本发明范围的方式属于下列组:羟基磷灰石,α-TCP,β-TCP和/或它们的组合,优选羟基磷灰石(HA)。
本发明的另一个特别目的由纳米复合粉末组成,其中包含按重量计0.01%至8%之间的金属银颗粒,最佳百分比为按重量计1%的银。
本发明的另一个目的由用于获得本发明纳米复合粉末的方法组成,所述方法在下文中称作本发明的方法,其包括下列步骤:
a.通过溶胶-凝胶加工途径制备纳米磷酸钙;以及
b.在所述磷酸钙表面上沉积银纳米颗粒。
本发明的另一个特别目的由本发明的方法组成,其中在步骤a)中,已经通过溶胶-凝胶法制备了磷酸钙,所述溶胶-凝胶法包括下列步骤:
a)利用必需量的亚磷酸三乙酯和硝酸钙制备相应的水溶液,从而在最终混合物中获得期望的Ca/P摩尔比,在羟基磷灰石的情况下优选为1.67;
b)在强烈搅拌、保持控制温度和pH条件的同时,向钙溶液中逐滴添加磷溶液;
c)搅拌所得的胶态悬浮体,随后在环境温度下老化优选24小时,从而形成凝胶;以及
d)在真空加热器中干燥所述凝胶直到完全除去溶剂,并在包括于500℃至1000℃之间,优选550℃的温度下进行煅烧,从而获得纳米尺寸且充分结晶的粉末。
本发明的另一个特别目的由本发明的方法组成,其中在步骤b)中,其包括下列步骤(方法1):
a)利用在6中获得的粉末制备含水悬浮体,将pH调节至5并以低浓度向其中添加阴离子表面活性剂;
b)在没有光的情况下,添加具有必需浓度的银盐前体的水溶液,参考磷酸钙固体含量,所述必需浓度使得在最终化合物中包含按重量计在0.01%至8%之间的元素银含量,优选按重量计1%的银;
c)强烈搅拌所述悬浮体,将pH调节至9,以这种方式使得Ag+阳离子析出为氧化物(Ag2O);
d)将所得粉末过滤,用蒸馏水洗涤并干燥;以及
e)在包括于150℃至500℃之间的温度范围内,优选在350℃下,在H2/Ar气氛中进行还原。
本发明的另一个特别目的由本发明的方法组成,其中在步骤b)中,其包括下列步骤(方法2):
a)利用在6中获得的羟基磷灰石粉末制备含水悬浮体,以低浓度向其中添加阴离子表面活性剂;
b)使用0.1N NaOH水溶液将pH调节至7;
c)施加超声波探头1-10分钟,并且在球磨机中完全均质化和破碎(粉碎,disintegration);
d)逐滴添加必需量的银前体溶液AgNO3以在最终产物中获得在最终化合物中包含按重量计在0.01%至8%之间的Ag0浓度,继续强烈搅拌10分钟,优选按重量计1%的银;
e)使用任何还原剂,优选NaBH4原位化学还原银,所述还原剂在继续强烈搅拌的同时被逐滴添加至分散液中;以及
f)过滤,用蒸馏水洗涤并在60℃下的加热器中干燥。
最后,本发明的另一个目的由本发明的纳米复合粉末在杀菌剂和/或杀真菌剂组合物的精心制作中的应用组成,所述杀菌剂和/或杀真菌剂组合物可以被用作用于下述应用的通用消毒剂,所述应用以实例且并不旨在限制本发明范围的方式属于下列组:外科植入、公共设施(卫生间和医院、运输工具等)、食品、牙科、油漆、衣服和包装(食品、药物、医疗设备)。
附图说明
图1是由透射电子显微镜法获得的显微照片,该显微照片显示了通过方法1获得的附着于羟基磷灰石纳米颗粒表面的银纳米颗粒的均匀分布,所述银纳米颗粒的尺寸小于20nm,所述羟基磷灰石纳米颗粒的尺寸为约140nm。
图2是由透射电子显微镜法获得的显微照片,该显微照片显示了通过方法2获得的纳米复合粉末,其中可以观察到Ag纳米颗粒的尺寸小于15nm。
具体实施方式的实施例
实施例1-用于获得本发明的纳米复合粉末的方法
下面详细描述了用于获得本发明的纳米复合粉末的方法,所述方法包括下述两个主要制备步骤:通过溶胶-凝胶加工途径制备纳米磷酸钙以及在所述磷酸钙表面上沉积银纳米颗粒。
1.1-作为磷酸钙的羟基磷灰石(HA)合成
用于合成HA的前体是亚磷酸三乙酯(98%,Aldrich)和硝酸钙四水合物(≥99%,Fluka)。下面详细陈列了接下来的方法:
1.使用必需量的这些前体制备相应的水溶液,从而在最终混合物中获得1.67的Ca/P摩尔比;
2.在强烈搅拌、保持控制温度和pH条件的同时,向钙溶液中逐滴添加亚磷酸三乙酯;
3.在搅拌下保持所得的胶态悬浮体,并在环境温度下老化24小时之后,形成凝胶;以及
4.在真空加热器中干燥所获得的凝胶直到完全除去溶剂。然后在550℃下对其进行煅烧,从而获得纳米尺寸且充分结晶的羟基磷灰石粉末,所述羟基磷灰石粉末的尺寸小于150nm。
1.2-银在所述HA纳米颗粒上的沉积方法
关于这点,通过两种不同方法获得了本发明的纳米结构粉末。
方法1
在通过溶胶-凝胶法和随后的煅烧来合成HA纳米颗粒之后,在利用最佳量的表面活性剂分散在水中的HA上发生根据前体(例如,硝酸银)的银氧化物的沉积。然后,在Ar/H2气氛中在烘箱中将阳离子Ag+还原成Ag0,如下面详细说明的:
a)利用在1.1中获得的羟基磷灰石粉末制备了含水悬浮体。在搅拌下将pH调节至5。为了获得羟基磷灰石的更好的分散,以低浓度引入阴离子表面活性剂作为分散剂(相对于以固体的羟基磷灰石浓度为按重量计1%);
b)在避光的情况下,添加银盐前体水溶液,所述银盐前体水溶液具有使得在最终HA-Ag化合物中包含按重量计在0.01%至8%之间的元素银含量的必需浓度(参考HA固体含量);
c)在强烈搅拌所述悬浮体的同时,将pH调节至9,以这种方式使得Ag+阳离子析出为氧化物(Ag2O);以及
d)在过滤和洗涤之后,将其在包括于150℃至500℃之间的温度范围内在Ar/10%H2气氛中干燥并还原。
由此获得了具有附着于羟基磷灰石纳米颗粒表面的银纳米颗粒的纳米复合粉末,所述银纳米颗粒的尺寸小于20nm且具有均匀分布,所述羟基磷灰石纳米颗粒的尺寸为约140nm。
方法2
在通过溶胶-凝胶法和随后的煅烧来合成HA纳米颗粒之后,根据分散在具有最佳pH和分散剂的水中的银前体在羟基磷灰石上沉积银纳米颗粒Ag0。在环境温度下使用还原剂进行原位还原。
a)利用获得的羟基磷灰石粉末制备了含水悬浮体。为了获得羟基磷灰石的更好的分散,以低浓度引入阴离子表面活性剂作为分散剂(Dolapix);
b)为了获得HA颗粒的良好分散并同时避免Ag+离子作为Ag2O的沉淀,使用0.1N NaOH水溶液将pH调节至7,所述沉淀在高于8的pH值下发生;
c)施加超声波探头1-10分钟,并且在球磨机中均质化和破碎;
d)为了在最终产物中获得在最终HA-Ag化合物中包含按重量计在0.01%至8%之间的Ag0浓度,添加必需量的前体AgNO3。一旦逐滴添加至HA分散液中,则在继续下一步骤之前强烈搅拌10分钟。该过程必须在添加所述前体之后,在保护所述前体溶液和所述分散液免受光的条件下实施;
e)使用例如NaBH4作为还原剂原位化学进行银还原,所述还原剂根据下列反应以1∶8(NaBH4∶Ag+)的摩尔比与银发生反应;
f)将NaBH4溶液逐滴添加(沉积,放置,deposite)到分散液中;以及
g)强烈搅拌,过滤,用蒸馏水洗涤,最后在60℃下的加热器中干燥。
由此获得了本发明的纳米复合粉末,其中可以观察到,Ag纳米颗粒的尺寸小于15nm。
实施例2-本发明的纳米复合粉末的杀菌活性和浸出的试验
进行了杀菌试验以研究含银的样品对不同生物体大肠杆菌JM 110(革兰氏阴性菌)、藤黄微球菌(革兰氏阳性菌)和东方伊萨酵母(酵母)的作用。将微生物播种于用于大肠杆菌JM110和藤黄微球菌的陪氏培养皿上的Luria-Bertani(LB)固体培养基(包含:1%胰蛋白胨,0.5%酵母提取液,1%ClNa,1.5%琼脂)或酵母提取液葡萄糖(YEPD)(包含:1%酵母提取液,2%胨,2%葡萄糖)中。在37℃下将培养皿培育24小时。然后,将各种微生物的上述培养皿的分离的菌落接种至5mL LB(细菌)或YEPD(酵母)中,并在37℃下将其培养5小时以获得预培养。同时制备了包含1%银的制剂M1和M2的200mg/ml(重量/重量)的含水悬浮体。最后,将10μL的各种微生物的预培养物根据微生物而接种至1mL的LB或YEPD中。然后,将150μL的HA/nAg样品(M1和M2)添加至培养物中,从而获得按Ag重量计为0.13%的最终浓度。此外,准备了不含银的样品以出于对照目的,所述样品由水和相应培养基的混合物组成。在搅拌下在37℃下培养所述培养物,并在进行各自的连续稀释之后,从不同的培养物中取出用于活菌计数的等份。
2.1-利用藤黄微球菌进行的杀菌试验
利用使用方法1(将AgNO3用作银前体,且最终化合物HA-Ag的银含量按重量计为1%(参考HA固体含量))获得的HA粉末制备了含水悬浮体(按重量计9%的固体)。利用藤黄微球菌进行的试验在24小时之后显示了<1.0·104(或<1.0×104)的标题(title),而对照是3.0·109。
在72小时之后,发现浸出到培养基中的钙的浓度在15-30ppm的范围内。银的浓度<5ppm。与其相似,将作为商用纳米结构的银Vitelinate(卵黄磷蛋白银(Argenol),其粒度小于20nm)的相同起始浓度的银接种到其中,其后观察到浸出了约1300ppm的银。
2.2-利用大肠杆菌进行的杀菌试验
利用使用方法1(将AgNO3用作银前体,且最终化合物HA-Ag中的银含量按重量计为1%(参考HA固体含量))获得的HA粉末制备了含水悬浮体(按重量计9%的固体)。利用大肠杆菌JM 110进行的试验在24小时之后显示了<1.0·104的标题,而对照是1.4·1011。
在72小时之后,发现浸出到培养基中的钙的浓度在15-30ppm的范围内。银的浓度<5ppm。与其相似,将相同起始浓度的商用纳米结构银Vitelinate(卵黄磷蛋白银(Argenol),其粒度小于20nm)接种到其中,其后观察到浸出了约900ppm的银。
2.3-利用东方伊萨酵母进行的杀菌试验
利用使用方法2(将AgNO3用作银前体,且最终化合物HA-Ag中的银含量按重量计为1%(参考HA固体含量))获得的HA粉末制备了含水悬浮体(按重量计9%的固体)。利用东方伊萨酵母进行的杀菌试验在24小时之后显示了1.0·104的标题,而对照是1.2·1011。
在72小时之后,发现浸出到培养物中的钙的浓度在15-30ppm的范围内。银的浓度<5ppm。与其相似,将相同起始浓度的商用纳米结构银Vitelinate(卵黄磷蛋白银(Argenol),其粒度小于20nm)接种到其中,其后观察到浸出了约800ppm的银。
2.4-利用藤黄微球菌进行的杀菌试验
利用使用方法2(将AgNO3用作银前体,且最终化合物HA-Ag中的银含量按重量计为1%(参考HA固体含量))获得的HA粉末制备了含水悬浮体(按重量计9%的固体)。利用藤黄微球菌进行的杀菌试验在24小时之后显示了4.0·104的标题,而对照是3.0·109。
在72小时之后,发现浸出到培养物中的钙的浓度在15-30ppm的范围内。银的浓度<5ppm。与其相似,将相同起始浓度的商用纳米结构银Vitelinate(卵黄磷蛋白银(Argenol),其粒度小于20nm)接种到其中,其后观察到浸出了约900ppm的银。
2.5-利用大肠杆菌JM 110进行的杀菌试验
利用使用方法2(将AgNO3用作银前体,且最终化合物HA-Ag中的银含量按重量计为1%(参考HA固体含量))获得的HA粉末制备了含水悬浮体(按重量计9%的固体)。利用大肠杆菌JM 110进行的杀菌试验在24小时之后显示了<1.0·104的标题,而对照是1.4·1011。
在72小时之后,发现浸出至培养物中的钙的浓度在15-30ppm的范围内。银的浓度<5ppm。与其相似,将相同起始浓度的商用纳米结构银Vitelinate(卵黄磷蛋白银(Argenol),其粒度小于20nm)接种到其中,其后观察到浸出了约1300ppm的银。
Claims (9)
1.纳米复合粉末,其特征在于,所述纳米复合粉末由磷酸钙和附着于所述磷酸钙表面的Ag纳米颗粒形成,所述磷酸钙优选具有小于150nm的粒度,所述Ag纳米颗粒的尺寸优选小于50nm。
2.根据权利要求1所述的纳米复合粉末,其特征在于,所述磷酸钙属于下列组:羟基磷灰石、α-TCP、β-TCP和/或它们的组合。
3.根据权利要求1所述的纳米复合粉末,其特征在于,所述磷酸钙为羟基磷灰石(HA)。
4.根据权利要求1所述的纳米复合粉末,其特征在于,包含按重量计在0.01%至8%之间的金属银颗粒含量,优选按重量计1%的银。
5.一种用于获得根据权利要求1至4所述的纳米复合粉末的方法,其特征在于,所述方法包括下列步骤:
a)通过溶胶-凝胶加工途径制备纳米磷酸钙;以及
b)在磷酸钙表面上沉积银纳米颗粒。
6.根据权利要求5所述的方法,其特征在于,在步骤a)中,已经通过溶胶-凝胶法制备了磷酸钙,所述溶胶-凝胶法包括下列步骤:
a)利用必需量的亚磷酸三乙酯和硝酸钙制备相应的水溶液,从而在最终混合物中获得期望的Ca/P摩尔比,在羟基磷灰石的情况下优选为1.67;
b)在强烈搅拌、保持控制温度和pH条件的同时,向钙溶液中逐滴添加磷溶液;
c)搅拌所得的胶态悬浮体,随后在环境温度下老化优选24小时,以形成凝胶;以及
d)在真空加热器中干燥所述凝胶直到完全除去溶剂,并在包括于500℃至1000℃之间,优选550℃的温度下进行煅烧,以获得纳米尺寸且充分结晶的粉末。
7.根据权利要求5所述的方法,其特征在于,在步骤b)中,包括下列步骤:
a.利用在6中获得的粉末制备含水悬浮体,将pH调节至5,并且其中以低浓度添加阴离子表面活性剂;
b.在没有光的情况下,添加具有必需浓度的银盐前体的水溶液,参考磷酸钙固体含量,所述必需浓度使得在最终化合物中包含按重量计在0.01%至8%之间的元素银含量,优选按重量计1%的银;
c.强烈搅拌所述悬浮体,将pH调节至9,以这种方式使得Ag+阳离子析出为氧化物Ag2O;
d.将所得粉末过滤,用蒸馏水洗涤并干燥;以及
e.在包括于150℃至500℃之间的温度范围内,优选在350℃下,在H2/Ar气氛中进行还原。
8.根据权利要求5所述的方法,其特征在于,在步骤b)中,包括下列步骤:
a)利用在6中获得的羟基磷灰石粉末制备含水悬浮体,以低浓度向其中添加阴离子表面活性剂;
b)使用0.1N NaOH水溶液将pH调节至7;
c)施加超声波探头1-10分钟,并且在球磨机中完全均质化和破碎;
d)逐滴添加必需量的银前体溶液AgNO3以在最终产物中获得在最终化合物中包含按重量计在0.01%至8%之间的Ag0浓度,继续强烈搅拌10分钟,优选按重量计1%的银;
e)使用任何还原剂,优选NaBH4原位化学还原银,所述还原剂在继续强烈搅拌的同时被逐滴添加至分散液中;以及
f)过滤,用蒸馏水洗涤并在60℃下的加热器中干燥。
9.根据权利要求1至4所述的纳米复合粉末在杀菌剂和/或杀真菌剂组合物的制备中的应用,所述组合物能够被用作用于属于下列组的应用的消毒剂:外科植入、公共设施(卫生间和医院、运输工具等)、食品、牙科、油漆、衣服和包装(食品、药物、医疗设备)。
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CN103289408A (zh) * | 2012-02-29 | 2013-09-11 | 刘芳 | 一种硅橡胶的制备方法 |
CN106914629A (zh) * | 2017-03-02 | 2017-07-04 | 扬州大学 | 一种磷酸钙/纳米银壳层复合材料的制备方法 |
CN107309437A (zh) * | 2017-07-07 | 2017-11-03 | 东北师范大学 | 一种金纳米星/磷酸钙纳米粒子及其制备方法 |
CN111226917A (zh) * | 2020-03-26 | 2020-06-05 | 深圳市亚微新材料有限公司 | 一种磷酸氢锆纳米银抗菌复合材料的制备方法 |
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EP2136621B1 (en) * | 2007-04-04 | 2013-05-08 | Perlen Converting AG | Antimicrobial material |
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JP2009046410A (ja) * | 2007-08-17 | 2009-03-05 | Naoyuki Kato | 抗菌組成物およびその製造方法 |
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CN103289408A (zh) * | 2012-02-29 | 2013-09-11 | 刘芳 | 一种硅橡胶的制备方法 |
CN106914629A (zh) * | 2017-03-02 | 2017-07-04 | 扬州大学 | 一种磷酸钙/纳米银壳层复合材料的制备方法 |
CN107309437A (zh) * | 2017-07-07 | 2017-11-03 | 东北师范大学 | 一种金纳米星/磷酸钙纳米粒子及其制备方法 |
CN111226917A (zh) * | 2020-03-26 | 2020-06-05 | 深圳市亚微新材料有限公司 | 一种磷酸氢锆纳米银抗菌复合材料的制备方法 |
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